Living Polymerization of <i>α</i>‐Amino Acid <i>N</i>‐Carboxyanhydrides (NCA) upon Decreasing the Reaction Temperature

Vayaboury, Willy; Giani, Olivia; Cottet, Hervé; Deratani, A.; Schué, François

doi:10.1002/marc.200400111

Cited by 168 publications

(144 citation statements)

References 35 publications

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“…Further insights into amine initiated NCA polymerizations were also reported in 2004 by the group of Giani and coworkers [44]. This group studied the polymerization of ε-trifluoroacetyl-L-lysine NCA, TFA-Lys NCA, in DMF using n-hexylamine initiator at different temperatures.…”

Section: Insert Equation 11mentioning

confidence: 76%

Synthesis and Self-Assembly of Well-Defined Block Copolypeptides via Controlled NCA Polymerization

Deming

2013

Hierarchical Macromolecular Structures: 60 Years After the Staudinger Nobel Prize II

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Section: Insert Equation 11mentioning

confidence: 76%

Synthesis and Self-Assembly of Well-Defined Block Copolypeptides via Controlled NCA Polymerization

Deming

2013

Hierarchical Macromolecular Structures: 60 Years After the Staudinger Nobel Prize II

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“…For that reason, efforts have been devoted to develop new approaches in order to overcome these drawbacks, such as, the use of heavy metal catalysts [75], high vacuum techniques (HVT) [76], primary amine hydrochloride salts [77], the combination of low temperature with primary amines [78], the use of silazane derivatives as initiators [79] or the optimisation of reaction conditions (pressure, temperature, etc.) [80,81]. However, all methods present limitations: HVTs require a complex and expensive experimental setup; hexamethyldisilazane (HMDS) amines are sensitive to hydrolytic reactions, or heavy metal catalysts must be carefully removed to avoid non-specific toxicity in biomedical applications.…”

Section: Scheme 1 Ring-opening Polymerisation Of α-Amino Acid N-carbmentioning

confidence: 99%

Peptide-Based Polymer Therapeutics

2014

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Abstract:Polypeptides are envisaged to achieve a major impact on a number of different relevant areas such as biomedicine and biotechnology. Acquired knowledge and the increasing interest on amino acids, peptides and proteins is establishing a large panel of these biopolymers whose physical, chemical and biological properties are ruled by their controlled sequences and composition. Polymer therapeutics has helped to establish these polypeptide-based constructs as polymeric nanomedicines for different applications, such as disease treatment and diagnostics. Herein, we provide an overview of the advantages of these systems and the main methodologies for their synthesis, highlighting the different polypeptide architectures and the current research towards clinical applications.

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“…Initially, polymerization of an amino acid, l-leucine in this case, using the N-carboxy anhydride method, [10] on a tris(2-aminoethyl)amine (TAEA) initiator yielded the tripodal polypeptide with primary amine termini (P1). It should be noted that this method was purposely chosen, as it yields a significant yet narrow molecular weight distribution of polypeptides.…”

mentioning

confidence: 99%

A Tripodal Peptidic Titanium Phosphonate as a Homochiral Porous Solid Medium for the Heterogeneous Enantioselective Hydration of Epoxides

Milo

Neumann

2010

Adv Synth Catal

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A porous, homochiral titanium-phosphonate material based on a tripodal peptide scaffold was used as a heterogeneous reaction medium for the enantioselective hydration (> 99%) of styrene oxide. This titanium-phosphonate material, which was shown to contain confined chiral spaces, was prepared by polymerization of l-leucine onto a tris(2-aminoethyl)amine initiator, followed by capping with phosphonate groups and completed by non-aqueous condensation with titanium isopropoxide. Circular dichroism confirmed that the peptide tethers yielded a secondary structure. X-ray powder diffraction and transmission electron microscopy supported by a semi-empirical model showed the likely formation of a porous, lamellar material that was quantified by nitrogen adsorption.Keywords: catalyst design; enantioselectivity; hydrolysis; organic-inorganic composites; peptidesThe common strategy to carry out asymmetric catalysis for the preparation of enantiomerically enriched products, a cornerstone of modern synthetic chemistry, is to design homogeneous (soluble) metal-based and more recently also organic catalysts comprised of chiral ligands. The advantages of using insoluble catalyst systems, especially related to the practicality of recovering expensive catalysts, have also led to considerable efforts in the area of asymmetric heterogeneous catalysis. The typical approach utilized in this area is the covalent or non-covalent immobilization of known homogeneous catalysts onto supports.[1] More recently, we have also seen the incorporation of chiral ligands and chiral complexes into metal-organic framework materials, that is chiral MOFs, to yield what has been termed self-supported catalysts. Here, polytopic chiral ligands having both catalytically active and cross-linking sites are used for preparing homochiral materials that can be used in self-supported heterogeneous catalysis. [2] Another observation related to asymmetric catalysis is that, in principle, by carrying out reactions in chiral reaction media, enantiomerically enriched products can be attained. Historically, in homogeneous chiral media only low levels of enrichment have been observed, [3] although recently chiral ionic liquids were used as solvents for reactions that yielded high enantioselectivities, presumably due to their ionic nature.[4] Quite surprisingly there have been no reports on the use of porous, heterogeneous and homochiral media for asymmetric transformations. A quite singular example of asymmetric catalysis using insoluble peptidic, but non-porous media, is the epoxidation of a,b-unsaturated ketones on polypeptides (JuliaColonna reaction). [5] Based on the assumption that a more confined chiral environment may induce improved enantioselectivity, in this research we were interested in preparing porous, homochiral materials that can be used as heterogeneous media for enantioselective transformations. This would be the first step in the development of a general methodology for the preparation of chiral products from racemic or prochiral substrat...

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Living Polymerization of α‐Amino Acid N‐Carboxyanhydrides (NCA) upon Decreasing the Reaction Temperature

Cited by 168 publications

References 35 publications

Synthesis and Self-Assembly of Well-Defined Block Copolypeptides via Controlled NCA Polymerization

Synthesis and Self-Assembly of Well-Defined Block Copolypeptides via Controlled NCA Polymerization

Peptide-Based Polymer Therapeutics

A Tripodal Peptidic Titanium Phosphonate as a Homochiral Porous Solid Medium for the Heterogeneous Enantioselective Hydration of Epoxides

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